JP3211641B2 - Conductive composition - Google Patents
Conductive compositionInfo
- Publication number
- JP3211641B2 JP3211641B2 JP24472895A JP24472895A JP3211641B2 JP 3211641 B2 JP3211641 B2 JP 3211641B2 JP 24472895 A JP24472895 A JP 24472895A JP 24472895 A JP24472895 A JP 24472895A JP 3211641 B2 JP3211641 B2 JP 3211641B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive composition
- weight
- present
- parts
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Glass Compositions (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Joining Of Glass To Other Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Resistance Heating (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、導電性組成物に関
するものである。[0001] The present invention relates to a conductive composition.
【０００２】[0002]
【従来の技術】従来より、自動車窓ガラスの曇り止め用
あるいは霜取り用熱線ヒータには、銀ペーストを用いた
格子状の熱線ヒータ、いわゆるデフロスタを用いてい
る。2. Description of the Related Art Hitherto, a grid-like hot wire heater using a silver paste, that is, a so-called defroster, has been used as a hot wire heater for defrosting or defrosting automotive window glass.
【０００３】熱線ヒータに用いられる銀ペーストは、銀
粉末と、ガラスフリットと、複合酸化物等からなる無機
顔料とを、有機ビヒクルによってペースト化したもので
ある。[0003] The silver paste used in the hot wire heater is obtained by forming a silver powder, a glass frit, and an inorganic pigment composed of a composite oxide or the like into a paste using an organic vehicle.
【０００４】また、熱線ヒータはこの銀ペーストを自動
車用ガラス基板に印刷し、焼き付けることによって製造
されている。A hot wire heater is manufactured by printing and baking this silver paste on a glass substrate for automobiles.
【０００５】この自動車用ガラス基板は、フロートガラ
ス工法で作製されるので、一方の面には薄いスズ（Ｓ
ｎ）の被膜が付与されている。したがって、この面に上
記の銀ペーストを印刷、焼き付けした場合には、製造さ
れる熱線ヒータは、茶色または黄褐色である銀アンバー
発色を呈する。また、他方の面、すなわちスズ被膜のな
い面に上記の銀ペーストを印刷、焼き付けした場合に
は、銀コロイドのガラスへの拡散により黄色発色を呈す
る。現在は、スズ被膜面側に熱線ヒータを付与した銀ア
ンバー発色が主流である。[0005] Since this automotive glass substrate is manufactured by a float glass method, thin tin (S) is formed on one surface.
The coating of n) is provided. Therefore, when the above-mentioned silver paste is printed and baked on this surface, the manufactured hot-wire heater exhibits a silver-amber color that is brown or yellow-brown. When the silver paste is printed and baked on the other surface, that is, the surface having no tin film, a yellow color is exhibited due to the diffusion of the silver colloid into the glass. At present, silver amber coloring in which a hot wire heater is provided on the tin film surface side is mainly used.
【０００６】ところで、この熱線ヒータは、当初高級車
種のオプションとして装備されており、熱線ヒータ装備
が目立つことがステイタスとなっていたが、近年熱線ヒ
ータが標準装備に近い普及率に上昇したため、ステイタ
スとしての魅力はなくなり、熱線ヒータを目立たないよ
うにするデザイン的要求がでてくるようになった。[0006] By the way, this hot-wire heater was initially provided as an option for high-end models, and it was a status that the hot-wire heater was conspicuous. Has become less attractive, and there has been a demand for design to make the hot-wire heater inconspicuous.
【０００７】[0007]
【発明が解決しようとする課題】ところが、従来の導電
性組成物による熱線ヒータでは、銀アンバー発色や黄色
発色であるため、外観上熱線ヒータを目立たなくするこ
とが困難であった。However, in the case of a conventional hot wire heater made of a conductive composition, it is difficult to make the hot wire heater inconspicuous in appearance due to silver amber coloring and yellow coloring.
【０００８】本発明の目的は、銀アンバー発色よりも濃
い暗褐色の色調を呈する熱線ヒータを形成することが可
能な導電性組成物を提供することにある。An object of the present invention is to provide a conductive composition capable of forming a hot wire heater exhibiting a dark brown color tone darker than silver amber.
【０００９】[0009]
【課題を解決するための手段】本発明は、上記のような
課題を解決するべく、導電性組成物を完成するに至っ
た。本発明の導電性組成物は、（Ａ）銀粉末と、（Ｂ）
ガラスフリットと、（Ｃ）有機ロジウムと、（Ｄ）無機
顔料と、（Ｅ）有機ビヒクルと、を含有し、前記（Ｃ）
の有機ロジウムは、前記（Ａ）銀粉末１００重量部に対
して、金属ロジウム換算で０．００００１〜０．０００
１重量部配合してなることに特徴がある。SUMMARY OF THE INVENTION In order to solve the above problems, the present invention has completed a conductive composition. The conductive composition of the present invention comprises: (A) silver powder;
Glass frit, and (C) an organic rhodium, and (D) an inorganic pigment, containing, and (E) an organic vehicle, wherein the (C)
Of organorhodium relative to 100 parts by weight of the silver powder (A)
To 0.00001 to 0.000 in terms of metal rhodium.
The feature is that 1 part by weight is blended .
【００１０】また、本発明の導電性組成物においては、
前記（Ｄ）の無機顔料は、酸化銅、酸化マンガン、酸化
鉄、酸化クロムのうち、少なくとも２種類からなる複合
酸化物を含むことが好ましい。Further, in the conductive composition of the present invention,
It is preferable that the inorganic pigment (D) contains a composite oxide composed of at least two of copper oxide, manganese oxide, iron oxide, and chromium oxide.
【００１１】また、本発明の導電性組成物においては、
前記（Ｄ）の無機顔料は、酸化銅、酸化マンガン、およ
び酸化鉄からなる複合酸化物と、酸化銅および酸化クロ
ムからなる複合酸化物とのいずれか一方または両方を含
むことがさらに好ましい。Further, in the conductive composition of the present invention,
More preferably, the inorganic pigment of (D) contains one or both of a composite oxide composed of copper oxide, manganese oxide, and iron oxide and a composite oxide composed of copper oxide and chromium oxide.
【００１２】[0012]
【００１３】また、本発明の導電性組成物においては、
前記（Ａ）の銀粉末１００重量部に対して、前記（Ｂ）
のガラスフリットを０．５〜１０重量部と、前記（Ｄ）
の無機顔料を１〜５重量部と、前記（Ｅ）の有機ビヒク
ルを１０〜４０重量部とを配合してなることが好まし
い。[0013] In the conductive composition of the present invention,
With respect to 100 parts by weight of the silver powder of (A), (B)
0.5 to 10 parts by weight of the glass frit of (D)
It is preferable to mix 1 to 5 parts by weight of the inorganic pigment and 10 to 40 parts by weight of the organic vehicle (E).
【００１４】[0014]
【発明の実施の形態】以下、本発明の実施の形態につい
て説明する。本発明の導電性組成物は、（Ａ）銀粉末
と、（Ｂ）ガラスフリットと、（Ｃ）有機ロジウムと、
（Ｄ）無機顔料と、（Ｅ）有機ビヒクルとを含有してい
る。Embodiments of the present invention will be described below. The conductive composition of the present invention comprises (A) silver powder, (B) glass frit, (C) organorhodium,
It contains (D) an inorganic pigment and (E) an organic vehicle.
【００１５】本発明の導電性組成物に用いられる（Ａ）
銀粉末は、銀粉の形状、粒径などには特に限定されな
い。例えば、形状は球形状、扁平状など、どのような形
状のものであっても使用でき、もちろん互いに異なる形
状のものを混合して用いても構わない。(A) used in the conductive composition of the present invention
The silver powder is not particularly limited in shape, particle size and the like of the silver powder. For example, any shape such as a spherical shape and a flat shape can be used, and of course, different shapes may be mixed and used.
【００１６】また、粒径についても特に限定はないが、
球形状粉としては、平均粒径が０．１〜５μｍのものが
好ましい。平均粒径が０．１μｍ未満の場合には、銀が
過焼結となり、ガラス基板に大きな焼結ストレスを与え
てしまう。一方、平均粒径が５μｍを越える場合には、
銀の焼結状態がポーラスになり、引張強度が低下してし
まう。また、扁平状粉としては、ＳＥＭ平均粒径が３〜
１０μｍのものが好ましい。ＳＥＭ平均粒径が３μｍ未
満の場合には、焼結銀による可視光の反射効果が低下
し、暗褐色が薄くなってしまう。一方、ＳＥＭ平均粒径
が１０μｍを越える場合には、銀の焼結を抑制するた
め、引張強度が低下してしまう。Although there is no particular limitation on the particle size,
The spherical powder preferably has an average particle size of 0.1 to 5 μm. If the average particle size is less than 0.1 μm, silver will be over-sintered, giving a large sintering stress to the glass substrate. On the other hand, when the average particle size exceeds 5 μm,
The sintered state of silver becomes porous, and the tensile strength decreases. Further, as the flat powder, the SEM average particle size is 3 to
Those having a thickness of 10 μm are preferred. When the SEM average particle size is less than 3 μm, the effect of reflecting the visible light by the sintered silver decreases, and the dark brown color becomes thin. On the other hand, when the SEM average particle size exceeds 10 μm, the sintering of silver is suppressed, so that the tensile strength decreases.
【００１７】本発明の導電性組成物に用いられる（Ｂ）
ガラスフリットは、例えば、本発明の導電性組成物が自
動車用の熱線ヒータの製造に用いられる場合には、焼き
付けられた熱線ヒータと基体である自動車用ガラス基板
とを強固に結合させるための成分である。(B) used in the conductive composition of the present invention
The glass frit is, for example, when the conductive composition of the present invention is used in the production of a hot wire heater for an automobile, a component for firmly bonding the baked hot wire heater to an automotive glass substrate as a base. It is.
【００１８】このガラスフリットは、基体であるガラス
基板の軟化点付近の温度で充分流動する性質を有してい
る限り、その組成などには特に限定なく使用できる。こ
のようなガラスフリットの好ましい具体例としては、例
えば、軟化点３８０〜６５０℃の硼珪酸鉛系ガラスフリ
ット、軟化点４７０℃〜６５０℃の硼珪酸亜鉛系ガラス
フリット、軟化点４３０〜６５０℃の硼珪酸ビスマス系
ガラスフリットなどを主成分としたガラスフリットが挙
げられる。The composition of the glass frit can be used without any particular limitation as long as it has the property of flowing sufficiently at a temperature near the softening point of the glass substrate as the substrate. Preferred specific examples of such a glass frit include, for example, a lead borosilicate glass frit having a softening point of 380 to 650 ° C, a zinc borosilicate glass frit having a softening point of 470 ° C to 650 ° C, and a softening point of 430 to 650 ° C. A glass frit containing a bismuth borosilicate glass frit as a main component is exemplified.
【００１９】上記ガラスフリットの使用量は、本発明の
導電性組成物を用いる物品に応じて変更すればよく、従
って、必ずしも限定する必要はないが、例えば、本発明
の導電性組成物が自動車用の熱線ヒータの製造に用いら
れる場合には、本発明の導電性組成物中の銀粉末１００
重量部に対して、０．５〜１０重量部含有することが好
ましい。使用量が０．５重量部未満の場合には、銀焼結
後の十分な引張強度が得られない。一方、１０重量部を
越える場合には、実用上十分な端子のはんだ付け性が得
られない。The amount of the glass frit to be used may be changed according to the article using the conductive composition of the present invention, and is not necessarily limited. For example, the conductive composition of the present invention may be used in an automobile. Used in the production of a hot wire heater for use in the present invention, the silver powder 100 in the conductive composition of the present invention.
It is preferably contained in an amount of 0.5 to 10 parts by weight based on parts by weight. If the amount is less than 0.5 parts by weight, sufficient tensile strength after silver sintering cannot be obtained. On the other hand, if it exceeds 10 parts by weight, practically sufficient solderability of the terminal cannot be obtained.
【００２０】本発明の導電性組成物に用いられる（Ｃ）
有機ロジウムは、本発明の導電性組成物を上記ガラス基
板に焼き付けたときの色調を安定的に暗褐色にするため
の成分である。有機ロジウムはこの導電性組成物を焼成
した後に、酸化コロイドになり、このときに銀アンバー
色をやや黒褐色に近づけるような発色性が得られる。(C) used in the conductive composition of the present invention
Organic rhodium is a component for stably darkening the color tone when the conductive composition of the present invention is baked on the glass substrate. The organic rhodium becomes an oxidized colloid after baking the conductive composition, and at this time, a color developing property such as bringing the silver amber color slightly closer to black brown is obtained.
【００２１】上記有機顔料の使用量は、自動車用の熱線
ヒータの製造に用いられる場合には、本発明の導電性組
成物中の銀粉末１００重量部に対して、金属ロジウム換
算で０．００００１〜０．０００１重量部含有すること
を要する。金属ロジウム含有量が０．００００１重量部
未満の場合には、濃発色化を補う効果が十分に得られな
い。一方、０．０００１重量部を超える場合には、発色
の濃色化への効果が飽和状態になるとともに、比抵抗上
昇の要因になってしまう。[0021] The amount of the organic pigments, when used in the production of hot-wire heater for automobile, of silver powder 100 parts by weight of the conductive composition of the present invention, a metal rhodium terms 0.00001 To 0.0001 parts by weight
Cost . When the content of the metal rhodium is less than 0.00001 part by weight, the effect of supplementing the deep color development cannot be sufficiently obtained. On the other hand, when the amount exceeds 0.0001 parts by weight, the effect of deepening the color development becomes saturated, and the specific resistance increases.
【００２２】また、本発明の導電性組成物に用いられる
（Ｄ）無機顔料は、（Ｃ）有機ロジウムの発色を補うも
のとして使用されており、本発明の導電性組成物を上記
ガラス基板に焼き付けたときの色調を暗褐色に調整する
ための成分である。このような無機顔料の具体例として
は、例えば、酸化銅、酸化マンガン、酸化鉄、酸化クロ
ムなどの酸化物を２種類以上含有する複合酸化物が挙げ
られる。これらの複合酸化物は単独で用いてもよいし、
２種類以上併用してもよい。さらに好ましくは、酸化
銅、酸化マンガン、および酸化鉄からなる複合酸化物
と、酸化銅および酸化クロムからなる複合酸化物との両
方あるいはいずれか一方を含むものであり、これらはい
ずれも黒色顔料として用いられ、本発明の導電性組成物
が上記ガラス基板上で暗褐色を呈するのに有効である。The (D) inorganic pigment used in the conductive composition of the present invention is used to supplement the color development of (C) organorhodium, and the conductive composition of the present invention is applied to the above glass substrate. It is a component for adjusting the color tone when baked to dark brown. Specific examples of such an inorganic pigment include, for example, a composite oxide containing two or more oxides such as copper oxide, manganese oxide, iron oxide, and chromium oxide. These composite oxides may be used alone,
Two or more types may be used in combination. More preferably, copper oxide, manganese oxide, and a composite oxide composed of iron oxide, and / or a composite oxide composed of copper oxide and chromium oxide containing both or any of these, as a black pigment It is effective for the conductive composition of the present invention to exhibit a dark brown color on the glass substrate.
【００２３】上記無機顔料の使用量は、本発明の導電性
組成物を用いる物品に応じて変更すればよく、従って、
必ずしも限定する必要はないが、例えば、本発明の導電
性組成物が自動車用の熱線ヒータの製造に用いられる場
合には、本発明の導電性組成物中の銀粉末１００重量部
に対して、１〜５重量部含有することが好ましい。使用
量が１重量部未満の場合には、有機ロジウムと共用した
場合でも暗褐色の色調まで濃くならない。一方、５重量
部を越える場合には、有機ロジウムが未添加でも発色性
は良好であるが、はんだ付け性が低下し、端子のはんだ
付け不良となる。The amount of the inorganic pigment used may be changed according to the article using the conductive composition of the present invention.
Although not necessarily limited, for example, when the conductive composition of the present invention is used for manufacturing a hot wire heater for an automobile, 100 parts by weight of the silver powder in the conductive composition of the present invention, It is preferable to contain 1 to 5 parts by weight. When the amount is less than 1 part by weight, the color does not become dark brown tones even when used in combination with organic rhodium. On the other hand, when the amount exceeds 5 parts by weight, the color developability is good even when the organic rhodium is not added, but the solderability is deteriorated and the soldering of the terminal becomes poor.
【００２４】本発明の導電性組成物に用いられる（Ｅ）
有機ビヒクルは、上記（Ａ）銀粉末、（Ｂ）ガラスフリ
ット、（Ｃ）有機ロジウム、および（Ｄ）無機顔料の成
分をペースト化するための成分であり、このような有機
ビヒクルは特に限定されない。好ましい具体例として
は、例えば、エチルセルロース、ニトロセルロース、ア
ルキッド樹脂などを樹脂成分とし、ターピネオール、ブ
チルカルビトール、カルビトールアセテートなどを有機
溶剤として、樹脂成分の濃度が１〜４０％になるように
溶解したものなどが挙げられる。(E) used in the conductive composition of the present invention
The organic vehicle is a component for pasting the components of the (A) silver powder, (B) glass frit, (C) organic rhodium, and (D) inorganic pigment, and such an organic vehicle is not particularly limited. . As a preferred specific example, for example, ethyl cellulose, nitrocellulose, alkyd resin and the like are used as a resin component, and terpineol, butyl carbitol, carbitol acetate and the like are used as an organic solvent and dissolved so that the concentration of the resin component becomes 1 to 40%. And the like.
【００２５】上記有機ビヒクルの使用量は、本発明の導
電性組成物を用いる物品に応じて変更すればよく、従っ
て、必ずしも限定する必要はないが、例えば、本発明の
導電性組成物が自動車用の熱線ヒータの製造に用いられ
る場合には、本発明の導電性組成物中の銀粉末１００重
量部に対して、１０〜４０重量部含有することが好まし
い。使用量が１０重量部未満の場合には、ペースト状態
が得られない。一方、４０重量部を越える場合には、焼
成後の銀膜厚が薄くなりすぎて、端子はんだ付け時には
んだ食われによる強度劣化を生じてしまう。The amount of the organic vehicle to be used may be changed according to the article using the conductive composition of the present invention. Therefore, it is not necessary to limit the amount of the organic vehicle. When it is used for the production of a hot wire heater, it is preferable to contain 10 to 40 parts by weight based on 100 parts by weight of the silver powder in the conductive composition of the present invention. If the amount is less than 10 parts by weight, a paste state cannot be obtained. On the other hand, if it exceeds 40 parts by weight, the silver film thickness after firing becomes too thin, and the strength is deteriorated due to solder erosion at the time of terminal soldering.
【００２６】さらに、本発明の導電性組成物には、必要
ならば比抵抗値の調整のために、発色性、はんだ付け
性、端子引張強度等に影響することなく比抵抗値を任意
に上昇させることができる、有機Ｎｉ、有機Ｐｔなどの
抵抗値調整剤を配合してもよい。Furthermore, the conductive composition of the present invention may have a specific resistance value arbitrarily increased without affecting color development, solderability, terminal tensile strength, etc., if necessary, in order to adjust the specific resistance value. A resistance adjuster, such as organic Ni or organic Pt, which can be used, may be added.
【００２７】上記抵抗値調整剤の使用量は、本発明の導
電性組成物に応じて変更すればよく、従って、必ずしも
限定する必要はないが、例えば、本発明の導電性組成物
が自動車用の熱線ヒータの製造に用いられる場合には、
上記銀粉末１００重量部に対して、金属換算で０．１〜
５重量部配合することが好ましい。配合量が０．１重量
部未満の場合には、抵抗値上昇効果がほとんど得られな
い。一方、５重量部を越える場合には、銀の焼結を抑制
しすぎてはんだ食われが顕著になり、引張強度が大幅に
低下する。The amount of the above-mentioned resistance adjusting agent to be used may be changed according to the conductive composition of the present invention, and is not necessarily limited. For example, the conductive composition of the present invention may be used for automobiles. When used for the production of hot wire heaters,
0.1 to 100 parts by weight of the silver powder in terms of metal
It is preferable to mix 5 parts by weight. When the amount is less than 0.1 part by weight, the effect of increasing the resistance value is hardly obtained. On the other hand, when the amount exceeds 5 parts by weight, sintering of silver is suppressed too much, so that solder erosion becomes remarkable and tensile strength is significantly reduced.
【００２８】本発明の導電性組成物は、これら上記の成
分をあらかじめ混合し、混練させてペースト化すること
により、容易に作製することができる。The conductive composition of the present invention can be easily prepared by mixing the above components in advance, kneading the mixture, and forming a paste.
【００２９】このようにして作製された本発明の導電性
組成物は、ガラス基板に印刷、焼成してガラス基板のス
ズ被膜面より導体の色を観察すると、従来の銀アンバー
発色よりも濃い暗褐色を呈することが分かる。また、端
子との良好なはんだ付け性を有するものである。また、
１００Ｎ以上の充分な端子引っ張り強度を有し、さらに
は、高温高湿ライフテストにて±５％以内の抵抗変化率
に収まるものであり、実装上問題なく充分に使用でき
る。When the conductive composition of the present invention thus produced is printed on a glass substrate and fired, and the color of the conductor is observed from the tin-coated surface of the glass substrate, the darkness is darker than the conventional silver amber color. It turns out that it shows brown. Also, it has good solderability with terminals. Also,
It has a sufficient terminal tensile strength of 100 N or more, and falls within a resistance change rate of ± 5% or less in a high-temperature and high-humidity life test, and can be used satisfactorily without mounting problems.
【００３０】また、本発明の導電性組成物を用いて自動
車窓ガラスの曇り止め用あるいは霜取り用熱線ヒータを
製造する場合には、従来の導電性組成物を用いる方法と
同様の方法で用いればよく、例えば、上記のようにして
得られたペーストを自動車用ガラス基板上にスクリーン
印刷し、１３０〜１８０℃で５〜１０分間乾燥したの
ち、６００〜７００℃で１〜５分間焼き付けを行えばよ
い。In the case of producing a hot-wire heater for defrosting or defrosting automobile window glass using the conductive composition of the present invention, it is possible to use the same method as the conventional method using the conductive composition. For example, if the paste obtained as described above is screen-printed on an automotive glass substrate, dried at 130 to 180 ° C. for 5 to 10 minutes, and then baked at 600 to 700 ° C. for 1 to 5 minutes. Good.
【００３１】このようにして製造された熱線ヒータは、
車外から見た場合、暗褐色の色調を呈する。The hot wire heater manufactured in this manner is
It has a dark brown color when viewed from outside the vehicle.
【００３２】次に、本発明を実施例に基づき、さらに具
体的に説明するが、本発明はかかる実施例のみに限定さ
れるものではない。Next, the present invention will be described more specifically based on examples, but the present invention is not limited to only these examples.
【００３３】[0033]
【実施例】本実施例の導電性組成物は、（Ａ）銀粉末と
して、平均粒径０．１〜０．５μｍの球形状銀粉２０ｗ
ｔ％と、平均粒径１〜３μｍの球形状銀粉５０ｗｔ％
と、平均粒径３〜６μｍの扁平状銀粉３０ｗｔ％とを混
合した銀粉末を１００重量部用いている。EXAMPLE The conductive composition of the present example was prepared by using (A) silver powder 20 w of spherical silver powder having an average particle size of 0.1 to 0.5 μm as silver powder.
t%, 50 wt% spherical silver powder having an average particle size of 1 to 3 μm
And 100 parts by weight of silver powder obtained by mixing 30 wt% of flat silver powder having an average particle size of 3 to 6 μm.
【００３４】また、（Ｂ）ガラスフリットとして、軟化
点４６０℃の硼珪酸鉛系ガラスフリットを５重量部用い
ている。As the glass frit (B), 5 parts by weight of a lead borosilicate glass frit having a softening point of 460 ° C. is used.
【００３５】また、（Ｃ）有機ロジウムを表１に示す比
率で配合している。Further, (C) organorhodium is blended in the ratio shown in Table 1.
【００３６】また、（Ｄ）無機顔料として、黒色顔料で
あるＣｕＯ−ＭｎＯ2−Ｆｅ2Ｏ3系複合酸化物またはＣ
ｕＯ−Ｃｒ2Ｏ3系複合酸化物を表１に示す比率で配合し
ている。The inorganic pigment (D) may be a black pigment CuO—MnO 2 —Fe 2 O 3 -based composite oxide or C
The uO-Cr2O3-based composite oxide is blended in the ratio shown in Table 1.
【００３７】さらに、（Ｅ）有機ビヒクルとして、エチ
ルセルロースを樹脂成分の濃度が１０％となるようにタ
ーピネオールに溶解した有機ビヒクルを２５重量部用い
ている。Further, as the organic vehicle (E), 25 parts by weight of an organic vehicle obtained by dissolving ethyl cellulose in terpineol so that the concentration of the resin component becomes 10% is used.
【００３８】さらに、実施例５〜実施例７には、比抵抗
を上昇させる抵抗値調整剤として、有機Ｎｉ、有機Ｐｔ
を表１に示す比率で配合している。Further, in Examples 5 to 7, organic Ni and organic Pt were used as resistance adjusters for increasing the specific resistance.
Are blended at the ratios shown in Table 1.
【００３９】[0039]
【表１】 [Table 1]
【００４０】なお、参考例として、参考例１〜参考例３
を表１に併せて示す。これらは実施例１〜実施例１０で
用いたものと同一の銀粉末、ガラスフリット、および有
機ビヒクルを用い、さらに無機顔料および有機ロジウム
を表１に示す比率になるように用いた。As reference examples, reference examples 1 to 3 were used.
Are also shown in Table 1. The same silver powder, glass frit, and organic vehicle as those used in Examples 1 to 10 were used, and inorganic pigments and organic rhodium were used in the proportions shown in Table 1.
【００４１】そして、これら上記の成分をあらかじめ混
合し、混練させてペースト化した。得られたペースト
を、図１に示すように、フロートガラス工法で作製され
た自動車用ガラス基板３のスズ面側３ａに幅０．４ｍ
ｍ、平均長さ２００ｍｍのライン８本が平行に並んだ素
線５と、これらの両端に幅１０ｍｍのブスバー７ａ、７
ｂを配したパターンをスクリーン印刷し、６８０℃で３
分間焼成して熱線ヒータ１を製造した。The above components were mixed in advance and kneaded to form a paste. As shown in FIG. 1, the obtained paste was applied to the tin side 3a of the automotive glass substrate 3 manufactured by the float glass method by a width of 0.4 m.
m, an element wire 5 in which eight lines having an average length of 200 mm are arranged in parallel, and bus bars 7a, 7 having a width of 10 mm at both ends thereof.
screen-printed pattern with b
Heating for 1 minute produced the hot-wire heater 1.
【００４２】ここで、表２に、発色性、比抵抗、はんだ
付け性、端子引っ張り強度、強度ライフ、抵抗変化率の
測定（評価）結果を示す。Table 2 shows the results of measurement (evaluation) of color development, specific resistance, solderability, terminal tensile strength, strength life, and resistance change rate.
【００４３】[0043]
【表２】 [Table 2]
【００４４】まず、発色性については、自動車用ガラス
基板３上に設けられた熱線ヒータ１の色調を、熱線ヒー
タ１が設けられていない面から肉眼で観察し、暗褐色に
発色していた場合には○と評価し、そうでない場合には
×と評価した。First, with regard to the color development, the color tone of the hot-wire heater 1 provided on the glass substrate 3 for automobiles was observed with the naked eye from the surface where the hot-wire heater 1 was not provided, and the color was dark brown. Was evaluated as ○, and if not, evaluated as ×.
【００４５】実施例１〜実施例１０は、いずれも暗褐色
を呈しており、発色性が良好であった。Examples 1 to 10 all exhibited a dark brown color and had good coloring.
【００４６】一方、参考例１〜参考例３は、いずれも暗
褐色を呈しておらず、発色性が不良であった。これは、
有機ロジウムを添加していないために、暗褐色を呈する
には至らなかったからである。なお、参考例１〜参考例
３は、上記理由により発色性が充分でなく、本発明の目
的を達成することができないので、以下のはんだ付け
性、端子引っ張り強度、強度ライフ、および抵抗変化率
の測定および評価はしていない。On the other hand, all of Reference Examples 1 to 3 did not exhibit dark brown color and had poor coloring properties. this is,
This is because the addition of organorhodium did not result in a dark brown color. In addition, since reference example 1-reference example 3 do not have sufficient coloring property for the above-mentioned reason and cannot achieve the objective of the present invention, the following solderability, terminal tensile strength, strength life, and resistance change rate Is not measured and evaluated.
【００４７】次に、比抵抗については、図１に示す両ブ
スバー７ａ、７ｂ間の抵抗値と８本の素線５の膜厚を測
定して比抵抗を算出した。Next, regarding the specific resistance, the specific resistance was calculated by measuring the resistance value between the bus bars 7a and 7b and the film thickness of the eight strands 5 shown in FIG.
【００４８】次に、はんだ付け性および端子引っ張り強
度については、Ｓｎメッキ処理した真鍮端子をブスバー
７ａ、７ｂ上３ｍｍ四方の面積ではんだ付けして、はん
だ付け性の評価および端子引っ張り強度の測定を行っ
た。なお、はんだ付け性は、３ｍｍ四方の銀面の８０％
以上がはんだで覆われた場合には○と評価し、８０％未
満の場合には×と評価した。Next, regarding the solderability and the terminal tensile strength, the Sn-plated brass terminal was soldered on the bus bars 7a and 7b in an area of 3 mm square, and the solderability was evaluated and the terminal tensile strength was measured. went. The solderability is 80% of 3mm square silver surface.
When the above was covered with solder, it was evaluated as ○, and when less than 80%, it was evaluated as ×.
【００４９】実施例１〜実施例７は、いずれも８０％以
上がはんだで覆われており、はんだ付け性が良好であっ
た。また、端子引っ張り強度もいずれも１００Ｎ以上と
充分な強度を有しており、良好であった。In each of Examples 1 to 7, 80% or more was covered with the solder, and the solderability was good. In addition, the terminal tensile strength was 100 N or more, which was sufficient, and was good.
【００５０】一方、実施例８〜実施例１０は、いずれも
８０％未満とはんだが充分に覆われず、実施例１〜実施
例７よりも劣っていた。これは、無機顔料が５重量部よ
りも多く添加されていたために、はんだ付け性が低下し
たからである。なお、実施例８〜実施例１０は、上記理
由によりはんだ付け性の面で実施例１〜実施例７よりも
劣っているので、端子引っ張り強度、強度ライフ、およ
び抵抗変化率の測定はしていない。On the other hand, in each of Examples 8 to 10, the solder was not sufficiently covered at less than 80%, which was inferior to Examples 1 to 7. This is because the solderability was reduced because the inorganic pigment was added in an amount of more than 5 parts by weight. Note that Examples 8 to 10 are inferior to Examples 1 to 7 in terms of solderability for the above reasons, and therefore, the terminal tensile strength, the strength life, and the resistance change rate are measured. Absent.
【００５１】さらに、強度ライフおよび抵抗変化率につ
いては、真鍮端子をはんだ付けしたガラス試料を６０℃
９５％ＲＨの恒温恒湿槽に放置し、４週間後の端子引っ
張り強度を測定して強度ライフを求め、さらに１０００
時間後の抵抗変化率を測定し、強度と抵抗値の信頼性を
確認した。Further, regarding the strength life and the rate of change in resistance, a glass sample soldered with a brass terminal was heated at 60 ° C.
It was left in a constant temperature and humidity chamber of 95% RH, and the terminal tensile strength after 4 weeks was measured to determine the strength life.
The resistance change rate after time was measured, and the reliability of the strength and the resistance value was confirmed.
【００５２】実施例１〜実施例７は、いずれもあまり劣
化せず、充分な強度ライフを有しており、抵抗変化率も
±５％以内に収まっていた。Examples 1 to 7 did not deteriorate much, had a sufficient strength life, and had a resistance change rate within ± 5%.
【００５３】従って、実施例１〜実施例７は、いずれも
発色性、はんだ付け性、端子引っ張り強度、強度ライ
フ、および抵抗変化率で良好な結果を示し、実用上問題
なく使用できる充分な特性を示した。また、実施例８〜
実施例１０は、発色性については良好であったものの、
はんだ付け性の面で実施例１〜実施例７よりも劣ってい
た。さらに、参考例１〜参考例３は、少なくとも発色性
については不十分であり、本発明の目的を達成するには
至らなかった。Therefore, Examples 1 to 7 all show good results in color development, solderability, terminal tensile strength, strength life, and resistance change rate, and have sufficient characteristics that can be used without practical problems. showed that. Examples 8 to
In Example 10, although the color development was good,
It was inferior to Examples 1 to 7 in terms of solderability. Furthermore, Reference Examples 1 to 3 were at least insufficient in color development, and did not achieve the object of the present invention.
【００５４】[0054]
【発明の効果】本発明の導電性組成物を用いれば、銀ア
ンバー発色よりも濃い暗褐色の色調を呈する熱線ヒータ
を形成することが可能である。従って、自動車用の熱線
ヒータとして用いた場合、外観上目立たなくするという
デザイン的要求にも適合することが可能である。By using the conductive composition of the present invention, it is possible to form a hot-wire heater exhibiting a dark brown color tone darker than silver amber. Therefore, when used as a hot wire heater for automobiles, it is possible to meet the design requirement of making the appearance less noticeable.
【図１】本発明の導電性組成物を用いて熱線ヒータを形
成した自動車用ガラス基板を示す説明図。FIG. 1 is an explanatory view showing a glass substrate for an automobile in which a hot wire heater is formed using the conductive composition of the present invention.
１ 熱線ヒータ ３ 自動車用ガラス基板 ３ａ スズ被膜面 ５ 素線 ７ａ、７ｂ ブスバー DESCRIPTION OF SYMBOLS 1 Heat wire heater 3 Automotive glass substrate 3a Tin coating surface 5 Elemental wires 7a, 7b Busbar
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｈ０５Ｋ 1/09 Ｈ０５Ｋ 1/09 Ｚ (58)調査した分野(Int.Cl.7，ＤＢ名) H01B 1/22 H01B 1/16 C03C 8/16 - 8/18 C03C 27/12 C08L 1/08 C08L 67/08 H05K 1/09 ──────────────────────────────────────────────────の Continuing on the front page (51) Int.Cl. 7 identification code FI H05K 1/09 H05K 1/09 Z (58) Investigated field (Int.Cl. 7 , DB name) H01B 1/22 H01B 1 / 16 C03C 8/16-8/18 C03C 27/12 C08L 1/08 C08L 67/08 H05K 1/09
Claims (4)
重量部に対して、金属ロジウム換算で０．００００１〜
０．０００１重量部配合してなることを特徴とする 導電
性組成物。1. A and (A) silver powder, organic (B) and glass frit, and (C) an organic rhodium, and (D) an inorganic pigment, containing, and (E) an organic vehicle, wherein the (C) Rhodium is used in the above (A) silver powder 100
0.00001-
A conductive composition characterized by being added in an amount of 0.0001 part by weight .
マンガン、酸化鉄、酸化クロムのうち、少なくとも２種
類からなる複合酸化物を含むことを特徴とする請求項１
に記載の導電性組成物。2. The inorganic pigment according to claim 1, wherein the inorganic pigment contains a composite oxide composed of at least two of copper oxide, manganese oxide, iron oxide and chromium oxide.
3. The conductive composition according to 1.).
マンガン、および酸化鉄からなる複合酸化物と、酸化銅
および酸化クロムからなる複合酸化物とのいずれか一方
または両方を含むことを特徴とする請求項１または請求
項２に記載の導電性組成物。3. The inorganic pigment of (D) contains one or both of a composite oxide composed of copper oxide, manganese oxide and iron oxide and a composite oxide composed of copper oxide and chromium oxide. The conductive composition according to claim 1, wherein:
て、 前記（Ｂ）のガラスフリットを０．５〜１０重量部と、 前記（Ｄ）の無機顔料を１〜５重量部と、 前記（Ｅ）の有機ビヒクルを１０〜４０重量部と、 を配合してなることを特徴とする請求項１から請求項３
のいずれかに記載の導電性組成物。4. The glass frit of (B) is 0.5 to 10 parts by weight, and the inorganic pigment of (D) is 1 to 5 parts by weight with respect to 100 parts by weight of the silver powder of (A). , claim 3 and an organic vehicle 10-40 parts by weight, that by blending from claim 1, wherein the (E)
The conductive composition according to any one of the above.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24472895A JP3211641B2 (en) | 1995-09-22 | 1995-09-22 | Conductive composition |
| TW085110896A TW434576B (en) | 1995-09-22 | 1996-09-06 | Electrically-conductive composition |
| US08/711,806 US5795501A (en) | 1995-09-22 | 1996-09-10 | Electrically-conductive composition |
| KR1019960041322A KR100208211B1 (en) | 1995-09-22 | 1996-09-20 | Electrically conductive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24472895A JP3211641B2 (en) | 1995-09-22 | 1995-09-22 | Conductive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0992028A JPH0992028A (en) | 1997-04-04 |
| JP3211641B2 true JP3211641B2 (en) | 2001-09-25 |
Family
ID=17123019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24472895A Expired - Lifetime JP3211641B2 (en) | 1995-09-22 | 1995-09-22 | Conductive composition |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5795501A (en) |
| JP (1) | JP3211641B2 (en) |
| KR (1) | KR100208211B1 (en) |
| TW (1) | TW434576B (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000048642A (en) * | 1998-07-24 | 2000-02-18 | Murata Mfg Co Ltd | Conductive paste and glass circuit substrate |
| JP3484983B2 (en) * | 1998-07-28 | 2004-01-06 | 株式会社村田製作所 | Conductive paste and glass circuit board |
| JP2001135138A (en) * | 1999-10-29 | 2001-05-18 | Matsushita Electric Ind Co Ltd | Conductor paste |
| US6854386B2 (en) | 2000-10-31 | 2005-02-15 | International Imaging Materials Inc. | Ceramic decal assembly |
| US6796733B2 (en) | 2000-10-31 | 2004-09-28 | International Imaging Materials Inc. | Thermal transfer ribbon with frosting ink layer |
| JP3932858B2 (en) | 2001-10-23 | 2007-06-20 | 株式会社村田製作所 | Conductive paste |
| JP3767514B2 (en) * | 2002-04-26 | 2006-04-19 | 株式会社村田製作所 | Conductive paste |
| US6748997B2 (en) * | 2002-04-26 | 2004-06-15 | Haworth, Inc. | Reinforced support element for wall panel arrangement |
| JP4103672B2 (en) | 2003-04-28 | 2008-06-18 | 株式会社村田製作所 | Conductive paste and glass circuit structure |
| JP4645594B2 (en) * | 2004-07-06 | 2011-03-09 | 株式会社村田製作所 | Conductive paste and ceramic electronic component using the same |
| JPWO2006098160A1 (en) * | 2005-03-14 | 2008-08-21 | 株式会社村田製作所 | Conductive paste and glass structure |
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| US7462304B2 (en) * | 2005-04-14 | 2008-12-09 | E.I. Du Pont De Nemours And Company | Conductive compositions used in the manufacture of semiconductor device |
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| US7781493B2 (en) | 2005-06-20 | 2010-08-24 | Dow Global Technologies Inc. | Protective coating for window glass |
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| BRPI0719411B1 (en) * | 2006-12-19 | 2018-07-31 | Dow Global Technologies Inc. | Additive for a coating composition, method for improving the performance of a coating composition, method for coating a substrate, article, coating composition and kit for preparing a coating composition. |
| US7833439B2 (en) * | 2007-07-24 | 2010-11-16 | Ferro Corporation | Ultra low-emissivity (ultra low E) silver coating |
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| US7736546B2 (en) * | 2008-01-30 | 2010-06-15 | Basf Se | Glass frits |
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| KR20140032973A (en) * | 2011-01-14 | 2014-03-17 | 아사히 가라스 가부시키가이샤 | Windowpane for vehicles and method for producing same |
| US8398234B2 (en) | 2011-05-03 | 2013-03-19 | Kimberly-Clark Worldwide, Inc. | Electro-thermal antifog optical devices |
| JP5883116B2 (en) * | 2012-02-28 | 2016-03-09 | 京セラ株式会社 | Conductive paste for solar cell electrode, solar cell, and method for manufacturing solar cell |
| WO2019038846A1 (en) * | 2017-08-23 | 2019-02-28 | 日本碍子株式会社 | Method for producing optical component, and method for producing transparent sealing member |
| JP2020196869A (en) * | 2019-05-29 | 2020-12-10 | 三ツ星ベルト株式会社 | Conductive composition and metallized substrate and manufacturing method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5741763A (en) * | 1980-08-25 | 1982-03-09 | Tokyo Electric Co Ltd | Processing system of goods sales data |
| US4446059A (en) * | 1982-04-15 | 1984-05-01 | E. I. Du Pont De Nemours & Co. | Conductor compositions |
| JPS60176948A (en) * | 1984-02-21 | 1985-09-11 | Nippon Sheet Glass Co Ltd | Antifogging glass |
| JP2503974B2 (en) * | 1986-06-03 | 1996-06-05 | 株式会社村田製作所 | Conductive paste |
| JPH01258304A (en) * | 1988-04-06 | 1989-10-16 | Dai Ichi Kogyo Seiyaku Co Ltd | Conductive paste |
| JPH01258303A (en) * | 1988-04-06 | 1989-10-16 | Dai Ichi Kogyo Seiyaku Co Ltd | Conductive paste |
| JPH01258305A (en) * | 1988-04-06 | 1989-10-16 | Dai Ichi Kogyo Seiyaku Co Ltd | Silver paste excellent in conductivity |
| US5162062A (en) * | 1991-06-17 | 1992-11-10 | E. I. Du Pont De Nemours And Company | Method for making multilayer electronic circuits |
| US5378408A (en) * | 1993-07-29 | 1995-01-03 | E. I. Du Pont De Nemours And Company | Lead-free thick film paste composition |
| JP3541070B2 (en) * | 1994-11-15 | 2004-07-07 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Automotive glass thick film conductor paste |
| JP3063549B2 (en) * | 1994-11-25 | 2000-07-12 | 株式会社村田製作所 | Conductive paste |
-
1995
- 1995-09-22 JP JP24472895A patent/JP3211641B2/en not_active Expired - Lifetime
-
1996
- 1996-09-06 TW TW085110896A patent/TW434576B/en not_active IP Right Cessation
- 1996-09-10 US US08/711,806 patent/US5795501A/en not_active Expired - Lifetime
- 1996-09-20 KR KR1019960041322A patent/KR100208211B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0992028A (en) | 1997-04-04 |
| KR970017706A (en) | 1997-04-30 |
| US5795501A (en) | 1998-08-18 |
| KR100208211B1 (en) | 1999-07-15 |
| TW434576B (en) | 2001-05-16 |
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